Method of polymerizing fraction of gashouse oil drip containing indene and coumarone



group consisting of dialkyl sulphates and mono- Patented Jan. 4, 1944UNlTED- STATE S PATENT OFFICE METHOD OF POLYMEBIZING FRACTION F GASHOUSEOIL DRIP CONTAINING IN- DENE AND COUMABONE Solomon Caplan, New York, N.1., minor to Harvel Research Corporation, a corporation of New leraey fNo. 445,968

The present invention relates generally to a method of polymerizingorganic compounds having unsaturated carbon bonds and to the productsobtained thereby; and the present invention more particularly relates tothe polymerization of hydrocarbons having unsaturated bonds .by means ofdialkyl sulphates and monoalkyl acid sulphates.

It is an object of the present invention to obtain polymerization of anunsaturated organic compound by means of a sulphate which is soluble inthe organic compound.

Another object of the present invention is to use a dialkyl sulphatetopromote polymerization said unsaturated organic compound by means ofheat applied to the solution. 7

Another object of the present invention is to obtain the polymerizingaction of a sulphate compound on an unsaturated organic compound withoutthe disadvantages of the use of sulphuricacid.

It is further an object oi the present invention to polymerize thegeneral class of phenols having unsaturated alkylsubstituentgroups bymeans of alkyl sulphates, including monoalkyl acid sulphates and dialkylsulphates.

Other objects and advantages of the present invention will appear fromthe following disclosure of particulars of the present invention andfrom the claims appended hereto.

An advantage of the present invention is that dialkyl ulphates aresoluble in unsaturated organic compounds in amounts required forpolymerization, and that monoalkyl acid sulphates are partly soluble inunsaturated organic compounds. Further, monoalkyl acid sulphates andsulphuric acid, either or both together, are soluble in dlalkylsulphates and such solutions are soluble in unsaturated organiccompounds.

These solutions added to unsaturated organic compounds will causepolymerization of the unsaturated organic compounds when heat is used toproduce the polymerizing reaction.

The following are given as examples of unsaturated organic compoundswhose polymerization can be promoted by material selected from the 3Claims. (Cl. 260-81) alkylacid sulphates: acetylene; the unsaturatedcompounds in gas house drip and coal tar such as solvent naphtha,coumarone, indene, styrene, and so on; pine oil, limonene; citronellagrass oil, lemon grass oil, vetiver grass root oil and the various andseveral unsaturated alcohol and aldehyde constituents of these oils suchas geraniol, geranial, citronellal and citronellol; unsaturated fattyacid oils such as China-wood oil; unsaturated fatty acids such aslinoleic acid, linolic acid, and so on and the monoand poly-glyceridesof unsaturated fatty acids such as those found naturally in drying,semi-drying and non-drying oils, for example the monoand poly-glycoridesof linolic acid, linoleic acid and so on, whether taken from th naturalproduct or made artificially; cashew nut shell liquid and its phenolicconstituents and phenolic derivativesv such as cardol, anacardic acid}"Cardanol and other phenolic distillates, and also distillate residueshaving unsaturated side chains; marking nut shell liquid and itsphenolic constituents anacardol and the carboxylic phenols, its phenolicdistillates and phenolic distillate residues having unsaturated sidechains; Japanese lac and its phenolic constituents including urushiol;and in general those unsaturated organic compounds which can bepolymerized with concentrated or fuming sulphuric acid with the aid ofheat. It is here noted that the examples given which are phenols havingan ortho or the para position unsubstituted can be reacted with analdehyde, such for example as formaldehyde, either before, during orafter the polymerization by the methods of the present invention.

Examples of dialkyl and monoalkyl acid sulphates suitable for thepractice of the methods of the present invention the following aregiven: dimethyl sulphate, diethyl sulphate, dibutyl sulphate, dipropylsulphate, diamyl sulphate and the mixed-alkyl sulphates such as ethylbutyl sulphate, butyl amylsulphate, mono-ethyl acid 'sulphate,monopropyl acid sulphate, mono-isopropyl acid sulphate and so on.

Examples or particular applications of the methods of the presentinvention are:

(1) To polymerize gum forming unsaturated organic compounds present inpetroleum oils such as are used for lubrication subjected to hightemperatures and removing the polymerization products from the part ofthe petroleum oils desired an unsaturated organic compound which can bepolymerized with concentrated sulphuric acid,

' charging the resulting solution into the body to be impregnated, andapplying heat to promote the polymerization of the unsaturated organiccompound by the dialkyl sulphate; and

(3) To make coumarone resins with the use of a dialkyl sulphate or of amonoalkyl acid sulphate, or to control the polymerization reaction ofconcentrated or fuming sulphuric acid in making coumarone resin bydissolving the concentrated or fuming sulphuric acid in a dialkyl 1-phate or a monoalkyl sulphate before adding to the material to bepolymerized such as coumarone, indene, or gas house drip.

Further, polymerization products made with monoalkyl acid sulphates anddialkyl sulphates, particularly with the latter, are lighter in colorthan those made with sulphuric acid alone due apparently to the factthat the reaction is more gentle and gradual than the sudden heatproduced when sulphuric acid alone reacts. The same or similar advantageis attendant upon the useof a solution of sulphuric acid in a dialkylsulphate for polymerization because the sulphuric acid acts as though itwere not released for the polymerization reaction until a correspondingamount of the solvent dialkyl sulphate is used up, and, as pointed outabove, the reaction of the dia-lkyl sulphate is much more gradual thanthat of sulphuric acid alone, the gradual release of the sulphuric acidalso serving to control the rate of the polymerizing reaction.

The solutions of polymerizable unsaturated organic compoundsand alk ylsulphates, both the dialkyl sulphates andthe 'monoalkyl acid sulphates,are stable at normal temperatures, that is polymerization does not takeplace until heat is applied. There are several advantages to this amongwhich is the suitability of such a solution for making impregnations andthen promoting .the polymerization reaction by apof styrene are mixedfive parts of diethyl sulphate and the solution heated for three hoursat 140 C. and then for three hours at 120 C.

A hard brittle resin is formed which is suitable for use in lacquers,varnishes and in molded compositions. 1

Example III.-Into one hundred parts by weight of a fraction of gas housedrip oil bolling between 150 C. and 200 C. and containing indene andcoumarone were dissolved five parts of diethyl sulphate and the solutionheated for three hours at 140 C. and then for three hours at 120 C., ahard brittle resin being obtained which is suitable for use in lacquers,varnishes, molded compositions, and for other uses to which cumar resinis used.

lhe products of the method of the present invention are polymers of thematerials used for. producing them, that is, the products of the methodsof the present invention have higher molecular weights and highersoftening points than those of the materials used for producing them. Insome cases the polymerization has been carried on to a point wheresoftening of the product under heat does not take place beforecarbonization would occur.

With the methods of the present invention uniform polymerizationthroughout the mass being treated can be obtained more easily than withthe use of concentrated or fuming sulphuric acid and local burning orcharring does not occur. With the methods of the present invention thereis also the advantage that sulphur dioxide is not produced in suchheavyvolume 'as with concentrated sulphuric acid or fuming sulphuric acid. I

The particular examples of the methods of the present invention and ofexamples of the application of the methods of the present inventionplication of heat after the material has been properly impregnated.Another advantage is that complete and thorough mixing of the twomaterials can be made at normal temperatures and before heat is appliedto promote polymerization. Also another advantage is that polymerizationcan be carried on to a. desired degree to obtain a predeterminedviscosity after which polymerization is retarded or stopped by cooling.This advantage of stability at normal temperatures is also present incases where concentrated sulphuric acid is dissolved in an alkylsulphate and the resulting solution dissolved in a polymerizableunsaturated organic compound.

Examples of particular materials and methods used in the practice of thepresent invention are as follows: Y

Example I.--In one hundred parts by weight of China-wood oil, ten partsof diethyl sulphate were dissolved and the solution heated overnight atC. The product was a rubber mass suit- 'monly used for making varnishes,and for other purposes.

Example II.--Into one hundred parts by weight are given as illustrationstoward the adding and teaching of the methods of the present inventionto the art and are not for the limitation of the claims hereof.

The present application is a division of my copending application SerialNo. 291,902, filed August 25, 1939, which in turn is a division of myapplication Serial No. 109,469, filed November 8, 1936, now Patent No.2,176,058, issued O'ctober 17, 1939. 50

Having thus described my invention, what claim and desire to protect byLetters Patent 1. The method which comprises dissolving from about twoparts to about ten parts by weight of diethyl sulphate in one hundredparts of a fraction of gas house 011 drip, boiling between about 150 C.and about 200 C. and containing indene and coumarone and heating thesolution between about C. and about C. to*produce polymerization.

2. The method of making a resin which comprises dissolving a dialkylsulphate in a mixture of coumarone and indene and heating to producepolymerization.

3. The method of making a resin which comprises dissolving a dialkylsulphate in coumarone

